Visible light activation enables desulfonylative cross-coupling of glycosyl sulfones

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(12), P. 967 - 974

Published: Sept. 22, 2022

Language: Английский

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Direct synthesis of unprotected aryl C-glycosides by photoredox Ni-catalysed cross-coupling

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(3), P. 251 - 260

Published: Jan. 16, 2023

Language: Английский

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Diversification of Glycosyl Compounds via Glycosyl Radicals

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(38)

Published: June 7, 2023

Glycosyl radical functionalization is one of the central topics in synthetic carbohydrate chemistry. Recent advances metal-catalyzed cross-coupling chemistry and metallaphotoredox catalysis provided powerful platforms for glycosyl diversification. In particular, discovery new precursors conjunction with these advanced reaction technologies have significantly expanded space compound synthesis. this Review, we highlight most recent progress area starting from 2021, reports included will be categorized based on different types better clarity.

Language: Английский

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StereoselectiveC‐Aryl Glycosylation by Catalytic Cross‐Coupling of Heteroaryl Glycosyl Sulfones

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(18)

Published: March 7, 2023

Stereoselective C-glycosylation reactions are increasingly gaining attention in carbohydrate chemistry because they enable glycosyl precursors, readily accessible as anomeric mixtures, to converge a single diastereomeric product. However, controlling the stereochemical outcome through transition-metal catalysis remains challenging, and methods that leverage bench-stable heteroaryl sulfone donors facilitate glycosylation rare. Herein, we show two complementary nonprecious metal catalytic systems, based on iron or nickel, which capable of promoting efficient C-C coupling between sulfones aromatic nucleophiles electrophiles distinct mechanisms modes activation. Diverse C-aryl glycosides were secured with excellent selectivity, scope, functional-group compatibility, reliable access both α β isomers was possible for key sugar residues.

Language: Английский

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Direct radical functionalization of native sugars

Nature, Journal Year: 2024, Volume and Issue: 631(8020), P. 319 - 327

Published: June 19, 2024

Abstract Naturally occurring (native) sugars and carbohydrates contain numerous hydroxyl groups of similar reactivity 1,2 . Chemists, therefore, rely typically on laborious, multi-step protecting-group strategies 3 to convert these renewable feedstocks into reagents (glycosyl donors) make glycans. The direct transformation native complex saccharides remains a notable challenge. Here we describe photoinduced approach achieve site- stereoselective chemical glycosylation from widely available sugar building blocks, which through homolytic (one-electron) chemistry bypasses unnecessary group masking manipulation. This process is reminiscent nature in its regiocontrolled generation transient glycosyl donor, followed by radical-based cross-coupling with electrophiles activation light. Through selective anomeric functionalization mono- oligosaccharides, this protecting-group-free ‘cap glycosylate’ offers straightforward access wide array metabolically robust compounds. Owing biocompatibility, the method was extended post-translational proteins.

Language: Английский

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N-glycoside synthesis through combined copper- and photoredox-catalysed N-glycosylation of N-nucleophiles

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(5), P. 623 - 632

Published: March 1, 2024

Language: Английский

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Recent advances in transition-metal-catalyzed glycosyl cross-coupling reactions

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(12), P. 3430 - 3470

Published: Nov. 8, 2022

Language: Английский

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Iron-mediated ligand-to-metal charge transfer enables 1,2-diazidation of alkenes

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Dec. 23, 2022

Given the widespread significance of vicinal diamine units in organic synthesis, pharmaceuticals and functional materials, as well privileged molecular catalysts, an efficient practical strategy that avoids use stoichiometric strong oxidants is highly desirable. We herein report application ligand-to-metal charge transfer (LMCT) excitation to 1,2-diazidation reactions from alkenes TMSN

Language: Английский

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Generation and Use of Glycosyl Radicals under Acidic Conditions: Glycosyl Sulfinates as Precursors

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(16)

Published: Feb. 10, 2023

We herein report a method that enables the generation of glycosyl radicals under highly acidic conditions. Key to success is design and use sulfinates as radical precursors, which are bench-stable solids can be readily prepared from commercial starting materials. This development allows installation units onto pyridine rings directly by Minisci reaction. further demonstrate utility this in late-stage modification complex drug molecules, including anticancer agent camptothecin. Experimental studies provide insight into reaction mechanism.

Language: Английский

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C‐GlycosideSynthesis Enabled by Nickel Catalysis

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(17), P. 2217 - 2236

Published: April 13, 2023

Comprehensive Summary C‐Glycosides are critical, naturally occurring products and medicinal candidates, extensive efforts have been made to explore efficient approaches for creating C‐glycosidic bonds. Transition‐metal‐catalysis, particularly nickel‐catalyzed C‐glycosylation reactions constitute a promising strategy. However, achieving stereoselective synthesis of α‐ β‐C‐glycosides has long‐standing challenge. To address this problem, variety nickel‐mediated strategies developed. This review highlights recent developments in the diastereoselective briefly summarizes mechanistic understandings these methods.

Language: Английский

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